WO2023106178A1 - セラミックス球形体およびその製造方法 - Google Patents

セラミックス球形体およびその製造方法 Download PDF

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WO2023106178A1
WO2023106178A1 PCT/JP2022/044138 JP2022044138W WO2023106178A1 WO 2023106178 A1 WO2023106178 A1 WO 2023106178A1 JP 2022044138 W JP2022044138 W JP 2022044138W WO 2023106178 A1 WO2023106178 A1 WO 2023106178A1
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ceramic
less
spherical body
volume
polishing
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French (fr)
Japanese (ja)
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神井康宏
中島穂嵩
澤越達哉
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Toray Industries Inc
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Toray Industries Inc
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Priority to CN202280076410.7A priority Critical patent/CN118265682A/zh
Priority to KR1020247013068A priority patent/KR20240118063A/ko
Priority to JP2022574110A priority patent/JPWO2023106178A1/ja
Publication of WO2023106178A1 publication Critical patent/WO2023106178A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/18—Details
    • B02C17/20—Disintegrating members
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/528—Spheres
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/963—Surface properties, e.g. surface roughness

Definitions

  • the present invention relates to a ceramic spherical body and a manufacturing method thereof.
  • Pulverizers such as ball mills, vibration mills, sand mills, and bead mills are widely used for pulverizing powders used in electronic material applications and when dispersing pigments in ink applications.
  • grinding media such as balls and beads (hereinafter sometimes referred to simply as "media") used for such grinders, sintered ceramics containing zirconia as a main component that is excellent in terms of abrasion resistance and impact resistance body is used.
  • the composition ratio of ZrO 2 and Y 2 O 3 is limited, and the amount of Al 2 O 3 and the amount of SiO 2 are controlled to improve durability and wear resistance.
  • a medium is disclosed (for example, Patent Literature 1). These ceramic spheres are polished after sintering to improve surface smoothness and wear resistance.
  • the media Before and after using these media, the media are sometimes washed with water, but in general, ceramic spheres whose main component is zirconia are hydrophobic, so when washed with water, they form lumps in water and contain air. For example, there was a problem that the washability was poor. In particular, micro-diameter media with a diameter of ⁇ 0.1 mm or less have a light weight and a large surface area. At the same time, some media was also discarded, creating a handling issue that resulted in loss.
  • micro-diameter media have a large surface area, the amount of wear due to collision between the media and the material to be dispersed when used for pulverization and dispersion, especially the initial wear that occurs at the beginning of use due to the unevenness of the media surface. As a result, there have been quality issues such as deterioration of product characteristics due to media components contaminating the material to be dispersed.
  • the object of the present invention is to provide a ceramic spherical body that has high hydrophilicity and suppresses the amount of wear during pulverization, and a method for producing the same.
  • the present invention mainly has the following configurations.
  • a ceramic spherical body containing zirconia as a main component The proportion of monoclinic crystals is 3.0% by volume or less, The proportion of tetragonal crystals is 80% by volume or more and 95% by volume or less, surface roughness Sa is 0.005 ⁇ m or more and 0.015 ⁇ m or less,
  • the ceramic spherical body according to any one of (1) to (3) above which has an average particle size of 10 ⁇ m or more and 150 ⁇ m or less.
  • a method for producing a ceramic spherical body according to any one of (1) to (4) above comprising a polishing step of polishing the surface of the spherical ceramic containing zirconia as a main component to obtain a polished spherical ceramic;
  • a method for producing ceramic spheres, comprising a heat treatment step of heat-treating the polished spherical ceramics at 100° C. to 1300° C. in this order, wherein the surface roughness Sa of the polished spherical ceramics is 0.005 ⁇ m or more and 0.015 ⁇ m or less.
  • the ceramic spherical body of the present invention it is possible to obtain a ceramic spherical body that has high hydrophilicity and suppresses the amount of wear during pulverization.
  • FIG. 2 is a schematic diagram showing chemical bonding on the surface of the ceramic spheres containing zirconia as a main component according to the present invention.
  • 1 shows infrared spectroscopic measurement results at 2500 to 4000 cm ⁇ 1 of ceramic spheres obtained in Examples and Comparative Examples.
  • the ceramic spherical body of the present invention is made of a ceramic sintered body containing zirconia as a main component.
  • a ceramic sintered body as a final product that is, a ceramic sintered body as an intermediate obtained through one or more sintering steps in the manufacturing process, other than grinding media, is generically referred to as ""intermediate sintered body”.
  • both the ceramic sintered body and the intermediate sintered body as final products are collectively referred to simply as "sintered body”.
  • the ceramic spheres of the present invention are obtained by spherically molding ceramic raw material powder (hereinafter sometimes simply referred to as "raw material powder") containing zirconia as a main component.
  • raw material powder ceramic raw material powder
  • “having zirconia as a main component” means that the ratio of zirconia is 90% by weight or more. It is preferable because strength can be obtained.
  • each component in ceramics can be obtained as follows. First, a ceramic sample is crushed using a universal testing machine, and about 0.3 g of the crushed piece is placed in a platinum crucible and melted with potassium hydrogen sulfate. This is dissolved in dilute nitric acid to give a constant solution, each metal element is quantified using ICP emission spectrometry, and the content is determined by converting it into an oxide.
  • the components of the ceramic spheres of the present invention may be expressed as metal elements or as oxides.
  • the ceramic spheres of the present invention contain yttria (Y 2 O 3 ), ceria (CeO 2 ), alumina (Al 2 O 3 ), magnesia (MgO), It preferably contains calcia (CaO) or the like. These function as stabilizers and can improve the strength and toughness of the ceramic spheres. Among them, it is preferable to contain yttria.
  • the yttria content is preferably 4.6/95.4 or more and 5.6/94.4 or less, more preferably 4.7/95.3 or more and 5.5, in terms of the weight ratio of yttria/zirconia in the ceramic spherical body. /94.5 or less.
  • the weight ratio of yttria/zirconia By setting the weight ratio of yttria/zirconia to 4.6/95.4 or more, the ratio of the monoclinic phase of zirconia is suppressed when sintered, and the amount of wear when used for pulverization is further suppressed. can be done. In addition, by setting the weight ratio of yttria/zirconia to 5.6/94.4 or less, the ratio of the cubic crystal layer increases, so that the ratio of the tetragonal crystal phase relatively decreases, and when used for pulverization, can further suppress the amount of wear.
  • the ratio (A / B) is 0.07 or more and 0.30 or less It is important to Conventional ceramic spheres have an A/B ratio as low as about 0.02 and exhibit hydrophobicity, resulting in poor washability. There was a problem that it was discarded together with the liquid.
  • A/B As a method for increasing A/B, heat treatment is performed on the grinding media after polishing at 100° C. to 1300° C. by the method described later. This is because, as shown in FIG.
  • Peak maximum values A and B can be obtained by the following method. First, a ceramic spherical body is set in an FT-IR apparatus, nitrogen purge is performed for 30 minutes, and then diffuse reflection FT-IR measurement is performed. At this time, an Au deposition film is used as a reference.
  • the Kubelka-Munk transformation ((1-R 2 )/2R) is performed on the relative diffuse reflectance R of the sample, which is the measurement result, and the hydrogen bonding OH group seen in the spectrum after the Kubelka-Munk transformation is
  • the ceramic spheres of the present invention preferably have a water permeation rate of 2.0 ⁇ 10 ⁇ 4 g 2 /s or more and 80.0 ⁇ 10 ⁇ 4 g 2 /s or less by a permeation rate method.
  • the permeation rate is 2.0 ⁇ 10 ⁇ 4 g 2 /s or more, the ceramic spheres have good compatibility with water, and the hydrophilicity of the ceramic spheres is high, so that floating in water is further suppressed.
  • the permeation rate of water is more preferably 40.0 g 2 /s or more. The higher the permeation rate of water, the more hydrophilicity can be imparted.
  • the permeation rate can be calculated from the measurement results of the weight permeated by the solvent and the permeation time when the ceramic spheres are densely packed in a pipe-shaped column with a mesh on the bottom and immersed in the solvent.
  • the ceramic spherical body of the present invention has a tetragonal proportion of 80% by volume or more and 95% by volume or less.
  • the tetragonal crystals mutate into monoclinic crystals (pressure-induced transformation) when stress is applied, expanding in volume, suppressing cracks in the media, and reducing the amount of wear. Although it can be suppressed, if it is less than 80% by volume, the effect becomes small.
  • the proportion of tetragonal crystals is preferably at least 88% by volume.
  • the content of tetragonal crystals is more than 95% by volume, deterioration tends to occur in high-temperature water. Therefore, when the water temperature rises due to grinding and dispersion for a long time, the ceramic spheres may be damaged or worn. easier.
  • the proportion of tetragonal crystals is preferably 94% by volume or less.
  • the proportion of monoclinic crystals in the ceramic spherical body of the present invention is 3.0% by volume or less. If the proportion of monoclinic crystals is more than 3.0% by volume, the amount of wear increases.
  • the proportion of monoclinic crystals is preferably 2.0% by volume or less, more preferably 1.0% by volume or less. The lower the monoclinic ratio, the better, but it tends to increase due to the energy required in the polishing process and the heat during drying.
  • the ceramic spherical body of the present invention preferably has a cubic crystal fraction of 5% by volume or more and 20% by volume or less.
  • the proportion of tetragonal crystals is relatively increased, and an increase in the amount of wear due to pressure-induced transformation can be further suppressed.
  • the proportion of cubic crystals is 5% by volume or more, deterioration (phase transition from tetragonal crystals to monoclinic crystals) is less likely to occur in high-temperature water, and the water temperature rises by performing pulverization and dispersion for a long time. In this case, damage or wear of the ceramic spherical body can be further suppressed.
  • the ceramic spheres of the present invention have a monoclinic ratio of 9.0% by volume or less after a pressure cooker test (PCT) by wet heat treatment for 72 hours continuously at a temperature of 121° C. and a humidity of 100%. is preferred.
  • PCT pressure cooker test
  • Zirconia is known to transform from a tetragonal crystal to a monoclinic crystal when immersed in a solvent having a hydroxyl group such as water or alcohol.
  • the proportion of monoclinic crystals increases, and wear resistance deteriorates. It is possible to simulate the same phenomenon with a PCT device as an accelerated test. As a result of suppressing the generation, it is suitable as a dispersing medium.
  • Such monoclinic transformation due to hydrothermal deterioration tends to increase as the surface area of the ceramic spheres increases and the probability of contact with water molecules increases. It is preferable to finish the surface as smooth as possible with as few irregularities as possible.
  • the proportion of each crystal phase in the ceramic sphere can be measured by the powder X-ray diffraction method.
  • the ceramic spherical body of the present invention preferably has a surface roughness Sa (arithmetic average) of 0.005 ⁇ m or more and 0.015 ⁇ m or less.
  • a surface roughness Sa (arithmetic average) of 0.005 ⁇ m or more and 0.015 ⁇ m or less.
  • the surface roughness Sa is preferably 0.12 ⁇ m or less.
  • the surface roughness Sa can be measured by a laser microscope based on ISO 25178 (measurement method is JIS0681-6:2014).
  • a method of reducing the surface roughness Sa includes, for example, a method of surface-polishing a ceramic spherical body using a bead mill polishing device.
  • the ceramic spherical body of the present invention preferably has an average particle diameter X of 10 ⁇ m or more and 150 ⁇ m or less.
  • the average particle diameter X is 150 ⁇ m or less, the effect of improving hydrophilicity and suppressing floating in water becomes remarkable.
  • the average particle size X is 10 ⁇ m or more, ceramic spheres can be easily obtained by the currently established manufacturing method.
  • the average particle diameter X can be set within the above range by the sieve classification described later.
  • the ceramic spheres of the present invention can be produced by various methods. As an example, details of an example produced by a rolling granulation molding method will be described below.
  • the raw material powder can first be formed into spheres using a tumbling granulation method.
  • spherical granules are formed by alternately adding ceramic raw material powder and a liquid binder containing a binder and water to a rotating drum, and then interlocking the rotation. It is a method of producing a spherical molded body by applying the powder to fine particles and powder to grow the particles.
  • the sintered body that has undergone the sintering step can be used as a pulverizing media after undergoing grinding and low-temperature firing, which will be described later.
  • a hot isostatic pressurization step which will be described later.
  • the hot isostatic pressing step is further performed after the sintering step will be described below.
  • HIP treatment hot isostatic pressing treatment
  • a pressing step it is preferable to subject it to a pressing step.
  • HIP treatment is a treatment in which a high temperature and an isotropic pressure are applied to an object to be treated at the same time. Defects such as can be removed.
  • the HIP treatment is preferably performed at a temperature 0°C to 50°C lower than the sintering temperature in the sintering process. If the temperature is lower than that, the diffusion of the ceramic powder such as zirconia during the HIP process becomes insufficient, and defects may remain. On the other hand, if the temperature of the HIP treatment is higher than the sintering temperature, grain growth of the intermediate sintered body may lead to a decrease in strength and a large variation in strength.
  • the temperature of the HIP treatment is more preferably 0° C. to 40° C. lower than the sintering temperature in the sintering step, more preferably 0° C. to 30° C. lower.
  • the HIP treatment pressure should be sufficient to remove defects, and if the treatment is performed at a pressure of 100 MPa or more, it can be treated without problems. In order to obtain a high pressure state, it is preferable to process in an Ar gas atmosphere.
  • the surface roughness Sa (arithmetic mean) of the polished spherical ceramics obtained by the polishing step is 0.005 ⁇ m or more and 0.015 ⁇ m or less.
  • the surface roughness Sa is larger than 0.015 ⁇ m, the initial wear amount of the finally obtained ceramic spheres increases quadratically.
  • the surface roughness Sa can be measured by a laser microscope based on ISO 25178 (measurement method is JIS0681-6:2014).
  • Methods for polishing the surface of spherical ceramics include barrel polishing and polishing with a bead mill. Among them, polishing by a bead mill is preferable because it can obtain a ceramic spherical body with more suppressed wear. By performing polishing with a bead mill, polishing can be performed with higher energy, ceramic spheres having smoother surfaces can be obtained, and the amount of wear can be further suppressed.
  • Heat treatment process Further, a heat treatment process is applied to the polished ceramic spheres. Hydrophilicity can be imparted to the ceramic spheres by the heat treatment step. This is because the adsorbed water 1 (H 2 O) adhering to the ZrO 2 surface as shown in FIG. is. 2Zr-O + HO ⁇ 2Zr-OH The presence of the isolated Zr--OH groups 4 and the hydrogen-bonding OH groups 3 improves the hydrophilicity of the ceramic spheres. Further, by performing this heat treatment step after polishing, the surface state of the ceramic spheres described above is maintained, making it easier to exhibit hydrophilicity.
  • the temperature of the heat treatment step is preferably 100°C to 1300°C.
  • the temperature of the heat treatment step is 100° C. or higher, the effect of imparting hydrophilicity to the ceramic spheres is enhanced.
  • the temperature of the heat treatment step is 1300° C. or less, it is possible to further suppress the increase in the surface roughness Sa and the increase in the amount of wear during pulverization.
  • the ratio of monoclinic crystals tends to increase and the durability tends to decrease within the temperature range of 100 to 1300°C. It is within the range of 1300°C.
  • the heat treatment is preferably performed in the presence of water vapor, preferably in an air atmosphere. Heat treatment in a high humidity atmosphere is more preferable.
  • a desired average particle size, minimum particle size and maximum particle size can be obtained by the classification process.
  • the classification method include sieve-type classification in which a mesh-like sieve is used for classification.
  • the sieve classification may be performed by stacking two sieves to separate coarse powder having a relatively large particle size and fine powder having a relatively small particle size in one operation.
  • Peak intensity ratio A/B by infrared spectroscopy The sample was packed in a container inside the FT-IR device, purged with nitrogen for 30 minutes, dried in the sample chamber, and then measured by infrared spectroscopy.
  • the measurement conditions are as follows.
  • Varian7000 manufactured by Varian
  • Accessory Diffuse reflectance measurement (Burns collector)
  • Light source Glover (SiC)
  • Detector DTGS Wavenumber resolution: 4 cm -1
  • Accumulation times 256 times
  • Measurement results are subjected to Kubelka-Munk transformation, peak maximum value (A) near wave number 3300 to 3500 cm -1 related to hydrogen bonding OH group, and 450 derived from Zr-O bond
  • the surface roughness Sa was measured by the following method. Using a laser microscope (Keyence VK-X-150) with a 150x objective lens, adjust the digital zoom so that the measurement range is X/3 ( ⁇ m) square with respect to the diameter X of the ceramic spherical body to be measured. Then, the arithmetic mean height Sa of 10 spherical bodies was measured with a laser. An average value of 10 samples was calculated and used as the surface roughness Sa.
  • Permeation rate of water Permeation rate was measured by the following method.
  • a column made of an aluminum pipe with an outer diameter of 9 mm, an inner diameter of 7 mm, and a height of 200 mm was attached to the bottom of a nylon mesh with an opening of 18 ⁇ m.
  • the column was placed in a vial bottle with a height of 65 mm so that the bottom surface of the column was immersed in water, and the weight of the column alone was measured every 30 seconds.
  • the amount of weight change in the measurement result was taken as the permeation weight of water, and the relationship (W 2 /t) between the square of the permeation weight of water (W 2 ) and the permeation time (t) was calculated by the method of least squares to obtain the permeation rate.
  • Average Particle Size The particle size was measured by the following method. An aggregate of ceramic spheres was photographed with a digital microscope (VHX-2000 manufactured by Keyence) at a magnification of 10 to 200 times. Image analysis/measurement software (“WinROOF” (registered trademark) manufactured by Mitani Shoji Co., Ltd.) was used to binarize the brightness of the image for measurement as a reference. The binarized image was separated into circular figures by means of least squares, and the diameter of each separated circle was calculated as the diameter of each ceramic sphere. The number average value of the diameters of 1000 ceramic spheres was defined as the average particle diameter X.
  • WinROOF registered trademark
  • the number average value of the diameters of 1000 ceramic spheres was defined as the average particle diameter X.
  • Floating amount of ceramic spheres was measured by the following method. 20 ml of water was put into a disposable cup having an inner diameter of 52 mm and a height of 70 mm, and 10 g of the ceramic spheres obtained in Examples and Comparative Examples were charged at 1 g/s from above. The cup was then stirred for 30 seconds and the floating beads were scooped up with a spoon, dried and weighed. As a ranking of evaluation results, 0.00 to 0.20 g is "1", 0.21 to 0.40 g is "2", 0.41 to 0.60 g is "3", 0.61 g or more is "4" ” and numbered. A smaller number indicates higher hydrophilicity.
  • Amount of idling wear In order to evaluate the amount of wear of the ceramic spheres obtained in Examples and Comparative Examples, the amount of wear was measured by the following method during a idling operation using only beads and a solvent. 121 g of ceramic spheres were placed in a microbead compatible bead mill (PCM-LR manufactured by Asada Iron Works Co., Ltd.) and stirred at a peripheral speed of 12 m/s while 1 L of pure water was circulated at a flow rate of 200 cc/min. After stirring for 2 hours, the ceramic spherical body was taken out and dried, and the weight Z [g] was measured.
  • PCM-LR microbead compatible bead mill
  • the wear amount is calculated by subtracting Zg from the original weight of 121 g, and the evaluation results are ranked as follows: 0.00 to 0.50 g is "1", 0.51 g to 1.00 g is "2", 1.01 g to 1 .50g was numbered "3" and 1.51g to 2.00g was numbered "4". A smaller number indicates less wear.
  • Crush load Crush load was measured by the following method as an index of durability against cracking and breakage of the ceramic spherical body.
  • a compressive load was applied to one ceramic sphere at a load rate of 5.0 gf/sec using a microcompression tester (MCT-510 manufactured by Shimadzu Corporation), and the load value at breakage was measured. The measurement was performed on 30 ceramic spheres, and the average value was adopted. The higher the numerical value, the less the risk of cracking or damage to the media that can be used.
  • Example 1 Yttrium chloride was added to zirconium oxychloride so that the mass ratio of yttria/zirconia in terms of oxide in the resulting ceramic spheres was 4.9/95.1, and a raw material powder was produced by coprecipitation.
  • the molded body obtained as described above After drying the molded body obtained as described above, it was fired at 1400°C for 2 hours to obtain an intermediate sintered body (sintering step). Thereafter, the intermediate sintered body was subjected to HIP treatment at 1380° C. and 120 MPa for 1.5 hours (hot isostatic pressing process). The obtained sintered body was surface-polished using a wet bead mill polisher at a peripheral speed of 14 m/s with an abrasive for 10 hours, and then subjected to sieve-type classification. Thereafter, the temperature was raised at 100° C./h in an air atmosphere, and heat treatment was performed at 100° C. for 1 hour to produce ceramic spherical bodies shown in Table 1.
  • Example 2-4, 6-14, Comparative Examples 1-6, 11-18 Ceramic spherical bodies were produced in the same manner as in Example 1, except that the heat treatment temperature, yttria/zirconia ratio, and average particle size were changed as shown in Table 1.
  • Example 5 After sieving, the ceramic spheres were heated in a tube furnace at a rate of 100° C./h while flowing nitrogen at 1 atm, and heat-treated at 1000° C. for 1 hour in the same manner as in Example 1. was made.
  • Example 9 A ceramic spherical body was produced in the same manner as in Example 1, except that in the polishing step, instead of the bead mill polishing, the surface was polished using a wet barrel polishing machine for 6 hours.
  • FIG. 2 shows the results of infrared spectroscopic measurement at 2500 to 4000 cm ⁇ 1 for Examples 2 and 5 and Comparative Example 1.
  • Comparative Examples 1, 11, and 15 in which no heat treatment was performed, the A/B was small, so the OH groups on the surface of the ceramic spheres were small, and the floating amount in water was large.
  • the crystallinity increased, the amount of wear increased.
  • Comparative Examples 4, 9, 10, 14, and 18 had a large (A/B) ratio and a low monoclinic ratio, but the surface roughness increased, resulting in a large amount of wear.
  • Examples 1 to 2, 7 to 8, 11 to 12 in which the heat treatment temperature is 200 ° C. or less have a monoclinic ratio of 9 after the hydrothermal test (temperature 121 ° C., humidity 100%, accelerated test for 72 hours).
  • the crushing load value after the hydrothermal test is generally maintained at the level before the test, making it suitable as a highly reliable media for long-term use. Available.

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  • Crushing And Grinding (AREA)
  • Compositions Of Oxide Ceramics (AREA)
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JPS6051617A (ja) * 1983-08-29 1985-03-23 Asahi Chem Ind Co Ltd イツトリウムを固溶した酸化ジルコニウム粉の製法
JP2006298711A (ja) * 2005-04-22 2006-11-02 Toray Ind Inc ＺｒＯ２質焼結体およびその製造方法、粉砕機用部材、粉砕機
WO2010067782A1 (ja) * 2008-12-11 2010-06-17 東ソー株式会社 表面が平滑なセラミックビーズおよびその製造方法
JP2017056429A (ja) * 2015-09-18 2017-03-23 株式会社ニッカトー ジルコニア質微小メディア
JP2018090433A (ja) * 2016-12-01 2018-06-14 公立大学法人大阪市立大学 ジルコニア焼結体
JP2018177550A (ja) * 2017-04-04 2018-11-15 新日本電工株式会社 高屈折率材用ジルコニア粉末及びその製造方法
JP2020075236A (ja) * 2018-09-18 2020-05-21 東レ株式会社 粉砕用メディアの製造方法および粉砕用メディア
JP2021155328A (ja) * 2020-03-27 2021-10-07 東レ株式会社 セラミックス球形体

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JP4048017B2 (ja) 2000-04-28 2008-02-13 株式会社ニッカトー 耐久性および耐摩耗性にすぐれたジルコニア質焼結体からなる粉砕・分散用メディア

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JPS6051617A (ja) * 1983-08-29 1985-03-23 Asahi Chem Ind Co Ltd イツトリウムを固溶した酸化ジルコニウム粉の製法
JP2006298711A (ja) * 2005-04-22 2006-11-02 Toray Ind Inc ＺｒＯ２質焼結体およびその製造方法、粉砕機用部材、粉砕機
WO2010067782A1 (ja) * 2008-12-11 2010-06-17 東ソー株式会社 表面が平滑なセラミックビーズおよびその製造方法
JP2017056429A (ja) * 2015-09-18 2017-03-23 株式会社ニッカトー ジルコニア質微小メディア
JP2018090433A (ja) * 2016-12-01 2018-06-14 公立大学法人大阪市立大学 ジルコニア焼結体
JP2018177550A (ja) * 2017-04-04 2018-11-15 新日本電工株式会社 高屈折率材用ジルコニア粉末及びその製造方法
JP2020075236A (ja) * 2018-09-18 2020-05-21 東レ株式会社 粉砕用メディアの製造方法および粉砕用メディア
JP2021155328A (ja) * 2020-03-27 2021-10-07 東レ株式会社 セラミックス球形体

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